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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Hydrogen-bonded framework structures in 4-[(4-chloro-3-nitro­benzo­yl)­hydrazinocarbon­yl]pyridinium chloride and N-3,5-di­nitro­benzoyl-N′-isonicotinoylhydrazine

aComplexo Tecnológico de Medicamentos Farmanguinhos, Av. Comandante Guaranys 447, Jacarepaguá, Rio de Janeiro, RJ, Brazil, bFundação Oswaldo Cruz, Far Manguinhos, Rua Sizenando Nabuco, 100 Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, dDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and eSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 13 February 2006; accepted 21 February 2006; online 18 March 2006)

In 4-[(4-chloro-3-nitro­benzo­yl)­hydrazino­carbon­yl]­pyridinium chloride, C13H10ClN4O4+·Cl, the component ions are linked into a three-dimensional framework structure by a combination of three N—H⋯Cl and five C—H⋯O hydrogen bonds. In N-3,5-dinitro­benzoyl-N′-iso­nicotinoyl­hydrazine, C13H9N5O6, the mol­ecules are linked into a three-dimensional framework structure by one N—H⋯O and three C—H⋯O hydrogen bonds, augmented by an aromatic ππ stacking inter­action.

Comment

As part of our continuing studies of the supramolecular structures of hydrazones, we now report the structures of the title compounds, (I)[link] and (II)[link]. These compounds were initially prepared as part of a programme to test their bactericidal activities, especially towards the Mycobacterium tuberculosis bacterium. Both compounds were found to exhibit significant activities, which will be reported elsewhere.

In each compound (Figs. 1[link] and 2[link]), the N atoms of the hydrazine unit exhibit only very modest pyramidalization; however, the overall conformations are very far from being planar, as the leading torsion angles (Table 3[link]) readily show. The most striking difference between the two conformations is provided by the C17—N17—N27—C27 torsion angles; in both compounds, the nitro groups are also twisted out of the planes of the adjacent aryl rings. Hence, each mol­ecule exhibits no inter­nal symmetry, so that the mol­ecules are chiral. However, in each of (I)[link] and (II)[link], the space group accommodates equal numbers of the two enantiomers

[Scheme 1]

Compound (I)[link] is a salt in which the pyridyl N atom is protonated. The component ions are linked into a three-dimensional framework by three N—H⋯Cl hydrogen bonds, all involving the Cl1 anion as the acceptor, and five independent C—H⋯O hydrogen bonds (Table 1[link]). The structure also contains two fairly short C—H⋯Cl contacts, again both involving the Cl1 anion. The three-dimensional nature of the supramolecular structure can be demonstrated most simply in terms of a sheet formed by the three N—H⋯Cl hydrogen bonds only, and the linking of adjacent sheets via a cyclic motif involving just one of the C—H⋯O hydrogen bonds.

Within the selected asymmetric unit (Fig. 1[link]), pyridinium atom N11 acts as a hydrogen-bond donor to the Cl1 anion. Hydrazine atom N17 in the cation at (x, y, z) acts as a hydrogen-bond donor to the anion at ([{1\over 2}] + x, [{3\over 2}]y, z), so forming a C12(9) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain of alternating cations and anions running parallel to the [100] direction and generated by the a-glide plane at y = [3\over4]. In addition, hydrazine atom N27 in the cation at (x, y, z) acts as a hydrogen-bond donor to the anion at ([{1\over 2}]x, y, [{1\over 2}] + z), forming a C12(5) chain of alternating cations and anions running parallel to the [001] direction and generated by the effective c-glide plane at x = [1\over4] arising from the combination of the A-face centring and the explicit b-glide plane at x = [1\over4]. The combination of the [100] and [001] chains generates a (010) sheet built from a single type of R66(24) ring (Fig. 3[link]).

Two (010) sheets pass through each unit cell, generated, respectively, by the a-glide planes at y = [1\over4] and y = [3\over4], and adjacent sheets are linked by pairs of short C—H⋯O hydrogen bonds forming a cyclic motif. Aryl atom C26 in the cation at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O2 in the cation at (1 − x, 1 − y, z), thus generating an R22(10) ring centred at ([1\over2], [1\over2], 0) (Fig. 4[link]). Propagation of this hydrogen bond then links all of the (010) sheets into a single framework structure, which is further reinforced by the other C—H⋯O hydrogen bonds to give a three-dimensional structure of considerable complexity.

Since there are also two short C—H⋯Cl contacts within the structure (Table 1[link]), the Cl1 anion at (x, y, z) is surrounded by atoms N11 at (x, y, z), N17 and C13 both at (−[{1\over 2}] + x, [3\over2]y, z), and N27 and C22 both at ([{1\over 2}]x, y, −[{1\over 2}] + z). The H⋯Cl distances are within the sums of the van der Waals radii, although the inter­action energies are probably small. Atoms Cl1, N17vii, N27viii and C22viii [symmetry codes: (vii) x − [{1\over 2}], −y + [{3\over 2}], z; (viii) −x + [{1\over 2}], y, z[{1\over 2}]] are effectively coplanar, and the overall coordination of atom Cl1 can be regarded as a distorted trigonal bipyramid, with atoms N11 and C13vii occupying the axial sites (Fig. 5[link]).

The mol­ecules of compound (II)[link] (Fig. 2[link]) are linked into a three-dimensional framework by a combination of one N—H⋯N hydrogen bond and three C—H⋯O hydrogen bonds (Table 2[link]), augmented by an aromatic ππ stacking inter­action. The formation of this rather complex framework can readily be analysed in terms of two one-dimensional substructures, each in the form of a chain of rings built from the co-operative inter­action of two hydrogen bonds.

Hydrazine atom N17 in the mol­ecule at (x, y, z) acts as a hydrogen-bond donor to the ring atom N11 in the mol­ecule at ([{1\over 2}] + x, [{3\over 2}]y, [{1\over 2}] + z), so forming a C(7) chain running parallel to the [101] direction and generated by the n-glide plane at y = [3\over4]. At the same time, pyridyl atom C12 in the mol­ecule at ([{1\over 2}] + x, [{3\over 2}] − y, [{1\over 2}] + z) acts as a hydrogen-bond donor to carbonyl atom O2 in the mol­ecule at (x, y, z), thereby forming a C(9) chain along [101]. The combination of these two hydrogen bonds then generates a C(7)C(9)[R22(8)] chain of rings along [101] (Fig. 6[link]).

The [101] chains of rings are linked into sheets by a simple chain motif running parallel to the [001] direction. Pyridyl atom C15 in the mol­ecule at (x, y, z) acts as a donor to carbonyl atom O2 in the mol­ecule at (x, y, −1 + z) in a nearly linear hydrogen bond, so generating by translation a C(8) chain running parallel to the [001] direction. The combination of the [101] chain of rings and the [001] chain generates a (010) sheet, whose formation is further augmented by a single ππ stacking inter­action. The nitrated C21–C26 aryl rings in the mol­ecules at (x, y, z) and (2 − x, 1 − y, 2 − z), which lie in adjacent [101] chains offset along [100], are strictly parallel, with an inter­planar spacing of 3.342 (2) Å; the ring-centroid separation is 3.519 (2) Å, corresponding to a ring offset of 1.102 (2) Å.

Two (010) sheets pass through each unit cell; they are related to one another by inversion and are generated by the n-glide planes at y = [1\over4] and y = [3\over4], respectively. Adjacent sheets are linked into a single continuous three-dimensional framework structure by the final C—H⋯O hydrogen bond. Pyridyl atom C13 in the mol­ecule at (x, y, z), which lies in the (010) sheet generated by the n-glide plane at y = [3\over4], acts as a hydrogen-bond donor to nitro atom O51 in the mol­ecule at (1 − x, 1 − y, 2 − z), which forms part of the (010) sheet generated by the n-glide plane at y = [1\over4], so generating by inversion an R22(24) ring centred at ([1\over2], [1\over2], 1). The combination of the two hydrogen bonds having atoms C13 and C15 as the donors then generates a chain of edge-fused centrosymmetric rings having R22(24) rings centred at ([1\over2], [1\over2], n) (n = zero or integer) and R44(24) rings centred at ([1\over2], [1\over2], [1\over2] + n) (n = zero or integer) (Fig. 7[link]).

[Figure 1]
Figure 1
The independent components of (I)[link], showing the atom-labelling scheme and the N—H⋯Cl hydrogen bond within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
The mol­ecule of (II)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3]
Figure 3
A stereoview of part of the crystal structure of (I)[link], showing the formation of a (010) sheet of R66(24) rings constructed from three independent N—H⋯Cl hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 4]
Figure 4
Part of the crystal structure of (I)[link], showing the formation of an R22(10) ring linking the cations in adjacent sheets. For the sake of clarity, the anions, and H atoms not involved in the motif shown, have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, z).
[Figure 5]
Figure 5
Part of the crystal structure of (I)[link], showing the coordination of the anion at (x, y, z). For the sake of clarity, H atoms that are bonded to C atoms but are not involved in the inter­actions shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}] − x, y, −[{1\over 2}] + z) and (−[{1\over 2}] + x, [{3\over 2}]y, z), respectively.
[Figure 6]
Figure 6
Part of the crystal structure of (II)[link], showing the formation of a C(7)C(9)[R22(8)] chain of rings along [101]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions ([{1\over 2}] + x, [{1\over 2}] − y, [{1\over 2}] + z) and (−[{1\over 2}] + x, [{1\over 2}]y, −[{1\over 2}] + z), respectively.
[Figure 7]
Figure 7
A stereoview of part of the crystal structure of (II)[link], showing the formation of a chain of edge-fused R22(24) and R44(24) rings along [001]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

Experimental

Substituted nitro­benzoyl chlorides were prepared by treating the appropriate carboxylic acid (1 g) with thionyl chloride (3 equivalents), N,N-dimethyl­formamide (0.1 equivalent) and dichloro­methane (20 ml) at room temperature, under stirring and in a dinitro­gen atmosphere. After 6–8 h, the excess of thionyl chloride was removed under reduced pressure to leave the crude acyl chloride, which was used without purification in a reaction with iso­nicotinoyl­hydrazine (isoniazid, 1 equivalent) and, in the preparation of (II)[link] only, triethyl­amine (1 equivalent) in tetra­hydro­furan (20 ml) at 340 K. Compound (I)[link] was purified by recrystallization from ethanol (m.p. 510–511 K, yield 88%). MS m/z: 320 [M − HCl]+. NMR (DMSO-d6): δ(H) 11.48 (1H, s, NH), 11.30 (1H, s, NH), 9.06 (2H, d, J = 4.5 Hz, H2 and H6), 8.63 (1H, s, H2′), 8.28 (1H, d, J = 5.5 Hz, H3 and H5), 8.27 (1H, d, J = 8.5 Hz, H6′), 8.01 (1H, d, J = 8.5 Hz, H5′); δ(C) 162.7, 162.6, 147.3, 145.8, 143.9, 132.5, 132.3, 132.0, 128.7, 124.8, 123.7. IR (KBr disk, cm−1): 3171 (NH), 1710 (CO), 1677 (CO). Compound (II)[link] was purified by column chromatography on silica gel, using as eluant a hexane/ethyl acetate gradient, followed by recrystallization from ethanol (m.p. 531–533 K, yield 81%). MS m/z: 331 (M+). NMR (DMSO-d6): δ(H) 11.67 (1H, s, NH), 11.61 (1H, s, NH), 9.15 (2H, s, H2 and H6 or H3 and H5), 9.05 (2H, d, J = 6.0 Hz, H2 and H6 or H3 and H5), 8.98 (1H, d, J = 5.5 Hz, H4′), 8.28 (1H, d, J = 5.5 Hz, H2′ or H6′), 8.19 (1H, d, J = 5.5 Hz, H2′ or H6′); δ(C) 162.6, 161.6, 148.3, 146.0, 143.6, 134.4, 127.7, 123.7, 121.6. IR (KBr disk, cm−1): 3153 (NH), 1718 (CO), 1683 (CO).

Compound (I)[link]

Crystal data
  • C13H10ClN4O4+·Cl

  • Mr = 357.15

  • Orthorhombic, A b a 2

  • a = 15.2414 (2) Å

  • b = 22.6430 (9) Å

  • c = 8.3783 (5) Å

  • V = 2891.4 (2) Å3

  • Z = 8

  • Dx = 1.641 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3204 reflections

  • θ = 2.9–27.5°

  • μ = 0.48 mm−1

  • T = 120 (2) K

  • Plate, yellow

  • 0.30 × 0.10 × 0.10 mm

Data collection
  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.870, Tmax = 0.954

  • 14651 measured reflections

  • 3204 independent reflections

  • 3013 reflections with I > 2σ(I)

  • Rint = 0.044

  • θmax = 27.5°

  • h = −17 → 19

  • k = −29 → 29

  • l = −10 → 9

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.074

  • S = 1.05

  • 3204 reflections

  • 208 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.035P)2 + 2.5382P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.25 e Å−3

  • Δρmin = −0.36 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1424 Friedel pairs

  • Flack parameter: 0.01 (5)

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N11—H11⋯Cl1 0.88 2.26 3.078 (2) 153
N17—H17⋯Cl1i 0.88 2.31 3.161 (2) 163
N27—H27⋯Cl1ii 0.88 2.33 3.176 (2) 162
C12—H12⋯O31iii 0.95 2.39 3.127 (3) 134
C16—H16⋯O2ii 0.95 2.27 2.988 (3) 132
C16—H16⋯O32iv 0.95 2.42 3.018 (2) 121
C25—H25⋯O1v 0.95 2.50 3.439 (3) 168
C26—H26⋯O2vi 0.95 2.33 3.204 (2) 152
C13—H13⋯Cl1i 0.95 2.67 3.607 (2) 170
C22—H22⋯Cl1ii 0.95 2.67 3.589 (2) 162
Symmetry codes: (i) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]; (ii) [-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]; (iii) [-x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (iv) x-1, y, z; (v) [x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]; (vi) -x+1, -y+1, z.

Compound (II)[link]

Crystal data
  • C13H9N5O6

  • Mr = 331.25

  • Monoclinic, P 21 /n

  • a = 7.4534 (2) Å

  • b = 22.1762 (6) Å

  • c = 8.1006 (2) Å

  • β = 96.4890 (16)°

  • V = 1330.35 (6) Å3

  • Z = 4

  • Dx = 1.654 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 3028 reflections

  • θ = 3.1–27.5°

  • μ = 0.14 mm−1

  • T = 120 (2) K

  • Block, yellow

  • 0.28 × 0.16 × 0.16 mm

Data collection
  • Nonius KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.932, Tmax = 0.979

  • 16762 measured reflections

  • 3028 independent reflections

  • 2754 reflections with I > 2σ(I)

  • Rint = 0.035

  • θmax = 27.5°

  • h = −9 → 8

  • k = −28 → 26

  • l = −10 → 10

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.099

  • S = 1.06

  • 3028 reflections

  • 217 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0419P)2 + 0.7643P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.22 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
N17—H17⋯N11ix 0.88 1.94 2.8194 (16) 175
C12—H12⋯O2x 0.95 2.50 3.2615 (16) 137
C13—H13⋯O51xi 0.95 2.49 3.1956 (17) 131
C15—H15⋯O2xii 0.95 2.40 3.3415 (16) 172
Symmetry codes: (ix) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (x) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]; (xi) -x+1, -y+1, -z+2; (xii) x, y, z-1.

Table 3
Selected torsion angles (°) for compounds (I) and (II)

  (I) (II)
C13—C14—C17—N17 1.8 (3) −32.02 (17)
C14—C17—N17—N27 −172.91 (17) −177.39 (10)
C17—N17—N27—C27 77.4 (3) −156.24 (12)
N17—N27—C27—C21 170.59 (16) 177.66 (10)
N27—C27—C21—C22 −14.3 (3) 15.36 (17)
C22—C23—N3—O31 −15.8 (3) 5.25 (18)
C24—C25—N5—O51 −18.90 (18)

For (I)[link], the systematic absences permitted Aba2 (= C2ca) or Cmca as possible space groups; Aba2 was selected and confirmed by the subsequent structure analysis. For (II)[link], the space group P21/n was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were positioned geometrically, with C—H distances of 0.95 Å and Uiso(H) values of 1.2Ueq(C). H atoms bonded to N atoms were allowed to ride at the sites located from the difference maps, with N—H distances of 0.88 Å and Uiso(H) values of 1.2Ueq(N). The correct orientation of the structure of (I)[link] with respect to the polar axis direction was established by means of the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter.

For both compounds, data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

As part of our continuing studies of the supramolecular structures of hydrazones, we now report the structures of the title compounds, (I) and (II). These compounds were initially prepared as part of a programme to test their bactericidal activities, especially towards the Mycobacterium tuberculosis bacterium. Both compounds were found to exhibit significant activities, which will be reported elsewhere.

In each compound (Figs. 1 and 2), the N atoms of the hydrazine unit exhibit only very modest pyramidalization; however, the overall conformations are very far from being planar, as the leading torsion angles (Table 3) readily show. The most striking difference between the two conformations is provided by the C17—N17—N27—C27 torsion angles; in both compounds, the nitro groups are also twisted out of the planes of the adjacent aryl rings. Hence, each molecule exhibits no internal symmetry, so that the molecules are chiral. However, in each of (I) and (II), the space group accommodates equal numbers of the two enantiomers

Compound (I) is a salt in which the pyridyl N atom is protonated. The component ions are linked into a three-dimensional framework by three N—H···Cl hydrogen bonds, all involving the Cl1 anion as the acceptor, and five independent C—H···O hydrogen bonds (Table 1). The structure also contains two fairly short C—H···Cl contacts, again both involving the Cl1 anion. The three-dimensional nature of the supramolecular structure can be demonstrated most simply in terms of a sheet formed by the three N—H···Cl hydrogen bonds only, and the linking of adjacent sheets via a cyclic motif involving just one of the C—H···O hydrogen bonds.

Within the selected asymmetric unit (Fig. 1), pyridinium atom N11 acts as a hydrogen-bond donor to the anion, Cl1. Hydrazine atom N17 in the cation at (x, y, z) acts as a hydrogen-bond donor to the anion at (1/2 + x, 3/2 − y, z), so forming a C12(9) (Bernstein et al., 1995) chain of alternating cations and anions running parallel to the [100] direction and generated by the a-glide plane at y = 3/4. In addition, hydrazine atom N27 in the cation at (x, y, z) acts as a hydrogen-bond donor to the anion at (1/2 − x, y, 1/2 + z), forming a C12(5) chain of alternating cations and anions running parallel to the [001] direction and generated by the effective c-glide plane at x = 1/4 arising from the combination of the A-face centring and the explicit b-glide plane at x = 1/4. The combination of the [100] and [001] chains generates a (010) sheet built from a single type of R66(24) ring (Fig. 3).

Two (010) sheets pass through each unit cell, generated, respectively, by the a-glide planes at y = 1/4 and y = 3/4, and adjacent sheets are linked by pairs of short C—H···O hydrogen bonds forming a cyclic centrosymmetric motif. Aryl atom C26 in the cation at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O2 in the cation at (1 − x, 1 − y, −z), thus generating by inversion an R22(10) ring centred at (1/2, 1/2, 0) (Fig. 4). Propagation of this hydrogen bond then links all of the (010) sheets into a single framework structure, which is further reinforced by the other C—H···O hydrogen bonds to give a three-dimensional structure of considerable complexity.

As a result of the two short C—H···Cl contacts within the structure (Table 1), the Cl1 anion at (x, y, z) is surrounded by atoms N11 at (x, y, z), N17 and C13 both at (−1/2 + x, 1.5 − y, z), and N27 and C22 both at (1/2 − x, y, −1/2 + z). The H···Cl distances are within the sums of the van der Waals radii, although the interaction energies are probably small. Atoms Cl1, N17i, N27ii and C22ii [symmetry codes: (i) −1/2 + x, 3/2 − y, z; (ii) 1/2 − x, y, −1/2 + z] are effectively coplanar and the overall coordination of atom Cl1 can be regarded as a distorted trigonal bipyramid, with atoms N11 and C13i occupying the axial sites (Fig. 5).

The molecules of compound (II) (Fig. 2) are linked into a three-dimensional framework by a combination of one N—H···N hydrogen bond and three C—H···O hydrogen bonds (Table 2), augmented by an aromatic ππ stacking interaction. The formation of this rather complex framework can readily be analysed in terms of two one-dimensional substructures, each in the form of a chain of rings built from the cooperative interaction of two hydrogen bonds.

Hydrazine atom N17 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the ring atom N11 in the molecule at (1/2 + x, 3/2 − y, 1/2 + z), so forming a C(7) chain running parallel to the [101] direction and generated by the n-glide plane at y = 3/4. A t the same time, pyridyl atom C12 in the molecule at (1/2 + x, 3/2 − y, 1/2 + z) acts as a hydrogen-bond donor to carbonyl atom O2 in the molecule at (x, y, z) thereby forming a C(9) chain along [101]. The combination of these two hydrogen bonds then generates a C(7)C(9)[R22(8)] chain of rings along [101] (Fig. 6).

The [101] chains of rings are linked into sheets by a simple chain motif running parallel to the [001] direction. Pyridyl atom C15 in the molecule at (x, y, z) acts as a donor to carbonyl atom O2 in the molecule at (x, y, −1 + z) in a nearly linear hydrogen bond, so generating by translation a C(8) chain running parallel to the [001] direction. The combination of the [101] chain of rings and the [001] chain generates a (010) sheet, whose formation is further augmented by a single π–.π stacking interaction. The nitrated aryl rings C21—C26 in the molecules at (x, y, z) and (2 − x, 1 − y, 2 − z), which lie in adjacent [101] chains offset along [100], are strictly parallel with an interplanar spacing of 3.342 (2) Å; the corresponding ring-centroid separation is 3.519 (2) Å, corresponding to a ring offset of 1.102 (2) Å.

Two (010) sheets pass through each unit cell; they are related to one another by inversion and they are generated by the n-glide planes at y = 1/4 and y = 3/4, respectively. Adjacent sheets are linked into a single continuous three-dimensional framework structure by the final C—H···O hydrogen bond. Pyridyl atom C13 in the molecule at (x, y, z), which lies in the (010) sheet generated by the n-glide plane at y = 3/4, acts as a hydrogen-bond donor to nitro atom O51 in the molecule at (1 − x, 1 − y, 2 − z), which forms part of the (010) sheet generated by the n-glide plane at y = 1/4, so generating by inversion an R22(24) ring centred at (1/2, 1/2, 1). The combination of the two hydrogen bonds having atoms C13 and C15 as the donors then generates a chain of edge-fused centrosymmetric rings having R22(24) rings centred at (1/2, 1/2, n) (n = zero or integer) and R44(24) rings centred at (1/2, 1/2, 1/2 + n) (n = zero or integer) (Fig. 7).

Experimental top

Substituted nitrobenzoyl chlorides were prepared by treating the appropriate carboxylic acid (1 g) with thionyl chloride (3 equivalents), N,N-dimethylformamide (0.1 equivalent) and dichloromethane (20 ml) at room temperature, under stirring and in a dinitrogen atmosphere. After 6–8 h, the excess of thionyl chloride was removed under reduced pressure to leave the crude acyl chloride, which was used without purification in a reaction with isonicotinoylhydrazine (isoniazid, 1 equivalent) and, in the preparation of (II) only, triethylamine (1 equivalent) in tetrahydrofuran (20 ml) at 340 K. Compound (I) was purified by recrystallization from ethanol (m.p. 510–511 K, yield 88%). MS m/z 320 [M-HCl]+. NMR (DMSO-d6): δ(H) 11.48 (1H, s, NH), 11.30 (1H, s, NH), 9.06 (2H, d, J = 4.5 Hz, H2 and H6), 8.63 (1H, s, H2'), 8.28 (1H, d, J = 5.5 Hz, H3 and H5), 8.27 (1H, d, J = 8.5 Hz, H6'), 8.01 (1H, d, J = 8.5 Hz, H5'); δ(C) 162.7, 162.6, 147.3, 145.8, 143.9, 132.5, 132.3, 132.0, 128.7, 124.8, 123.7. IR (KBr disk, cm−1) 3171 (NH), 1710 (CO), 1677 (CO). Compound (II) was purified by column chromatography on silica gel, using as eluant hexane/ethyl acetate gradient, followed by recrystallization from ethanol (m.p. 531–533 K, yield 81%). MS m/z 331 M+. NMR (DMSO-d6): δ(H) 11.67 (1H, s, NH), 11.61 (1H, s, NH), 9.15 (2H, s, H2 and H6 or H3 and H5), 9.05 (2H, d, J = 6.0 Hz, H2 and H6 or H3 and H5), 8.98 (1H, d, J = 5.5 Hz, H4'), 8.28 (1H, d, J = 5.5 Hz, H2' or H6'), 8.19 (1H, d, J = 5.5 Hz, H2' or H6'); δ(C) 162.6, 161.6, 148.3, 146.0, 143.6, 134.4, 127.7, 123.7, 121.6. IR (KBr disk, cm−1) 3153 (NH), 1718 (CO), 1683 (CO).

Refinement top

For compound (I), the systematic absences permitted Aba2 (= C2ca) or Cmca as possible space groups; Aba2 was selected, and confirmed by the subsequent structure analysis. For compound (II), the space group P21/n was uniquely assigned from the systematic absences. All H atoms were located in difference maps and then treated as riding atoms. H atoms bonded to C atoms were positioned geometrically, with C—H distances of 0.95 Å and Uiso(H) values of 1.2Ueq(C). H atoms bonded to N atoms were allowed to ride at the sites located from the difference maps, with N—H distances of 0.88 Å and Uiso(H) values of 1.2Ueq(N). The correct orientation of the structure of (I) with respect to the polar axis direction was established by means of the Flack (1983) parameter.

Computing details top

For both compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The independent components of (I), showing the atom-labelling scheme and the N—H···Cl hydrogen bond (dashed line) within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a (010) sheet of R66(24) rings constructed from three independent N—H···Cl hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation of a centrosymmetric R22(10) ring linking the cations in adjacent sheets. For the sake of clarity, the anions, and the H atoms not involved in the motif shown, have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, −z).
[Figure 5] Fig. 5. Part of the crystal structure of (I), showing the coordination of the anion at (x, y, z). For the sake of clarity, H atoms that are bonded to C atoms but not involved in the interactions shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 − x, y, −1/2 + z) and (−1/2 + x, 3/2 − y, z), respectively.
[Figure 6] Fig. 6. Part of the crystal structure of (II), showing the formation of a C(7)C(9)[R22(8)] chain of rings along [101]. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (1/2 + x, 1/2 − y 1/2 + z) and (−1/2 + x, 1/2 − y −1/2 + z), respectively.
[Figure 7] Fig. 7. A stereoview of part of the crystal structure of (II), showing the formation of a chain of edge-fused R22(24) and R44(24) rings along [001]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.
(I) 4-[(4-chloro-3-nitrobenzoyl)hydrazinocarbonyl]pyridinium chloride top
Crystal data top
C13H10ClN4O4+·ClF(000) = 1456
Mr = 357.15Dx = 1.641 Mg m3
Orthorhombic, Aba2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2acCell parameters from 3204 reflections
a = 15.2414 (2) Åθ = 2.9–27.5°
b = 22.6430 (9) ŵ = 0.48 mm1
c = 8.3783 (5) ÅT = 120 K
V = 2891.4 (2) Å3Plate, yellow
Z = 80.30 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
3204 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode3013 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
ϕ and ω scansh = 1719
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2929
Tmin = 0.870, Tmax = 0.954l = 109
14651 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.035P)2 + 2.5382P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3204 reflectionsΔρmax = 0.25 e Å3
208 parametersΔρmin = 0.36 e Å3
1 restraintAbsolute structure: Flack (1983), 1424 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (5)
Crystal data top
C13H10ClN4O4+·ClV = 2891.4 (2) Å3
Mr = 357.15Z = 8
Orthorhombic, Aba2Mo Kα radiation
a = 15.2414 (2) ŵ = 0.48 mm1
b = 22.6430 (9) ÅT = 120 K
c = 8.3783 (5) Å0.30 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
3204 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
3013 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 0.954Rint = 0.044
14651 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.25 e Å3
S = 1.05Δρmin = 0.36 e Å3
3204 reflectionsAbsolute structure: Flack (1983), 1424 Friedel pairs
208 parametersAbsolute structure parameter: 0.01 (5)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.07882 (10)0.67322 (8)0.5357 (2)0.0192 (4)
C120.14290 (12)0.70592 (9)0.4722 (3)0.0196 (4)
C130.22972 (11)0.69270 (9)0.5033 (3)0.0199 (4)
C140.24929 (13)0.64510 (8)0.6027 (3)0.0165 (4)
C150.18037 (12)0.61241 (10)0.6668 (3)0.0221 (4)
C160.09468 (12)0.62708 (10)0.6314 (3)0.0227 (4)
C170.34072 (12)0.62551 (9)0.6499 (2)0.0178 (4)
O10.35171 (9)0.58309 (7)0.7369 (2)0.0256 (3)
N170.40641 (10)0.65936 (8)0.5911 (2)0.0192 (4)
N270.49329 (10)0.64189 (7)0.6119 (2)0.0194 (3)
C270.52544 (12)0.59850 (8)0.5170 (2)0.0181 (4)
O20.47956 (9)0.57062 (6)0.42405 (18)0.0213 (3)
C210.62268 (12)0.58782 (8)0.5254 (2)0.0175 (4)
C220.68099 (12)0.62705 (9)0.5959 (3)0.0180 (4)
C230.77110 (12)0.61672 (9)0.5869 (3)0.0173 (4)
N30.82661 (10)0.66013 (7)0.6688 (2)0.0189 (4)
O310.79272 (9)0.70749 (7)0.7061 (2)0.0281 (4)
O320.90272 (9)0.64742 (7)0.70065 (19)0.0245 (3)
C240.80405 (12)0.56764 (9)0.5052 (3)0.0210 (4)
Cl40.91400 (3)0.55323 (3)0.47410 (8)0.03344 (15)
C250.74502 (13)0.52812 (9)0.4381 (3)0.0243 (4)
C260.65509 (13)0.53763 (9)0.4492 (3)0.0228 (4)
Cl10.07838 (3)0.72986 (2)0.36327 (6)0.02111 (11)
H110.02450.68320.51200.023*
H120.12870.73840.40530.023*
H130.27540.71570.45780.024*
H150.19240.57990.73520.027*
H160.04750.60470.67430.027*
H170.39890.68830.52230.023*
H270.52720.66080.67960.023*
H220.65950.66090.65020.022*
H250.76630.49420.38390.029*
H260.61550.50970.40460.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0104 (7)0.0246 (9)0.0226 (9)0.0012 (6)0.0006 (6)0.0009 (7)
C120.0141 (8)0.0213 (9)0.0232 (10)0.0002 (7)0.0008 (8)0.0030 (8)
C130.0126 (8)0.0213 (9)0.0259 (11)0.0019 (7)0.0003 (7)0.0007 (8)
C140.0110 (8)0.0198 (9)0.0187 (9)0.0008 (8)0.0006 (7)0.0017 (8)
C150.0142 (9)0.0260 (10)0.0260 (11)0.0000 (8)0.0006 (8)0.0062 (8)
C160.0130 (9)0.0274 (11)0.0277 (11)0.0026 (8)0.0026 (8)0.0040 (9)
C170.0124 (8)0.0193 (9)0.0215 (10)0.0007 (7)0.0010 (7)0.0026 (8)
O10.0159 (7)0.0268 (8)0.0340 (8)0.0012 (6)0.0013 (6)0.0093 (7)
N170.0075 (7)0.0206 (8)0.0296 (10)0.0010 (6)0.0020 (6)0.0027 (7)
N270.0075 (7)0.0233 (8)0.0273 (9)0.0012 (6)0.0033 (6)0.0031 (7)
C270.0124 (8)0.0178 (9)0.0242 (10)0.0014 (7)0.0003 (7)0.0051 (8)
O20.0140 (6)0.0219 (7)0.0281 (7)0.0043 (5)0.0038 (5)0.0024 (6)
C210.0126 (8)0.0189 (9)0.0209 (10)0.0019 (7)0.0010 (7)0.0022 (8)
C220.0131 (9)0.0190 (9)0.0219 (10)0.0000 (7)0.0005 (7)0.0017 (8)
C230.0114 (9)0.0187 (9)0.0217 (10)0.0017 (7)0.0016 (7)0.0010 (8)
N30.0125 (8)0.0225 (9)0.0218 (9)0.0019 (6)0.0009 (6)0.0008 (7)
O310.0164 (7)0.0246 (8)0.0433 (10)0.0006 (6)0.0025 (7)0.0124 (7)
O320.0107 (6)0.0304 (8)0.0323 (9)0.0000 (6)0.0053 (6)0.0005 (7)
C240.0113 (8)0.0229 (10)0.0288 (11)0.0017 (7)0.0004 (8)0.0005 (9)
Cl40.0122 (2)0.0351 (3)0.0531 (4)0.00455 (19)0.0001 (2)0.0154 (3)
C250.0192 (9)0.0178 (9)0.0358 (12)0.0015 (8)0.0005 (8)0.0049 (9)
C260.0162 (9)0.0206 (10)0.0314 (11)0.0030 (7)0.0015 (8)0.0025 (9)
Cl10.0150 (2)0.0240 (2)0.0243 (2)0.00446 (17)0.00164 (18)0.0037 (2)
Geometric parameters (Å, º) top
N11—C121.336 (2)N27—H270.8796
N11—C161.339 (3)C27—O21.222 (2)
N11—H110.8801C27—C211.503 (3)
C12—C131.382 (3)C21—C221.388 (3)
C12—H120.95C21—C261.394 (3)
C13—C141.394 (3)C22—C231.395 (3)
C13—H130.95C22—H220.95
C14—C151.393 (3)C23—C241.399 (3)
C14—C171.515 (3)C23—N31.467 (2)
C15—C161.380 (3)N3—O321.225 (2)
C15—H150.95N3—O311.231 (2)
C16—H160.95C24—C251.388 (3)
C17—O11.217 (2)C24—Cl41.7271 (19)
C17—N171.354 (3)C25—C261.390 (3)
N17—N271.393 (2)C25—H250.95
N17—H170.8801C26—H260.95
N27—C271.356 (3)
C12—N11—C16122.60 (16)N17—N27—H27120.1
C12—N11—H11117.1O2—C27—N27122.76 (17)
C16—N11—H11120.3O2—C27—C21120.73 (18)
N11—C12—C13120.33 (19)N27—C27—C21116.44 (17)
N11—C12—H12119.8C22—C21—C26119.31 (17)
C13—C12—H12119.8C22—C21—C27123.25 (17)
C12—C13—C14119.03 (17)C26—C21—C27117.32 (17)
C12—C13—H13120.5C21—C22—C23120.00 (18)
C14—C13—H13120.5C21—C22—H22120.0
C15—C14—C13118.69 (18)C23—C22—H22120.0
C15—C14—C17115.91 (18)C22—C23—C24120.86 (18)
C13—C14—C17125.39 (17)C22—C23—N3115.48 (17)
C16—C15—C14120.2 (2)C24—C23—N3123.66 (16)
C16—C15—H15119.9O32—N3—O31123.16 (17)
C14—C15—H15119.9O32—N3—C23119.39 (16)
N11—C16—C15119.18 (18)O31—N3—C23117.42 (15)
N11—C16—H16120.4C25—C24—C23118.54 (17)
C15—C16—H16120.4C25—C24—Cl4116.50 (16)
O1—C17—N17124.25 (18)C23—C24—Cl4124.91 (15)
O1—C17—C14120.94 (17)C24—C25—C26120.81 (19)
N17—C17—C14114.79 (17)C24—C25—H25119.6
C17—N17—N27119.79 (17)C26—C25—H25119.6
C17—N17—H17124.3C25—C26—C21120.41 (18)
N27—N17—H17114.6C25—C26—H26119.8
C27—N27—N17118.44 (16)C21—C26—H26119.8
C27—N27—H27121.3
C16—N11—C12—C130.3 (3)O2—C27—C21—C2612.8 (3)
N11—C12—C13—C140.4 (3)N27—C27—C21—C26169.94 (19)
C12—C13—C14—C150.1 (3)C26—C21—C22—C231.4 (3)
C12—C13—C14—C17179.2 (2)C27—C21—C22—C23174.34 (18)
C13—C14—C15—C160.3 (3)C21—C22—C23—C241.1 (3)
C17—C14—C15—C16179.7 (2)C21—C22—C23—N3178.53 (18)
C12—N11—C16—C150.1 (3)C22—C23—N3—O32162.21 (19)
C14—C15—C16—N110.4 (3)C24—C23—N3—O3217.4 (3)
C15—C14—C17—O11.1 (3)C22—C23—N3—O3115.8 (3)
C13—C14—C17—O1179.6 (2)C24—C23—N3—O31164.6 (2)
C15—C14—C17—N17177.54 (19)C22—C23—C24—C252.4 (3)
C13—C14—C17—N171.8 (3)N3—C23—C24—C25177.22 (19)
O1—C17—N17—N278.5 (3)C22—C23—C24—Cl4175.14 (16)
C14—C17—N17—N27172.91 (17)N3—C23—C24—Cl45.3 (3)
C17—N17—N27—C2777.4 (3)C23—C24—C25—C261.2 (3)
N17—N27—C27—O26.6 (3)Cl4—C24—C25—C26176.54 (18)
N17—N27—C27—C21170.59 (16)C24—C25—C26—C211.3 (3)
O2—C27—C21—C22163.0 (2)C22—C21—C26—C252.6 (3)
N27—C27—C21—C2214.3 (3)C27—C21—C26—C25173.4 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···Cl10.882.263.078 (2)153
N17—H17···Cl1i0.882.313.161 (2)163
N27—H27···Cl1ii0.882.333.176 (2)162
C12—H12···O31iii0.952.393.127 (3)134
C16—H16···O2ii0.952.272.988 (3)132
C16—H16···O32iv0.952.423.018 (2)121
C25—H25···O1v0.952.503.439 (3)168
C26—H26···O2vi0.952.333.204 (2)152
C13—H13···Cl1i0.952.673.607 (2)170
C22—H22···Cl1ii0.952.673.589 (2)162
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x+1/2, y, z+1/2; (iii) x+1, y+3/2, z1/2; (iv) x1, y, z; (v) x+1/2, y+1, z1/2; (vi) x+1, y+1, z.
(II) N-3,5-dinitrobenzoyl-N'-isonicotinoylhydrazine top
Crystal data top
C13H9N5O6F(000) = 680
Mr = 331.25Dx = 1.654 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3028 reflections
a = 7.4534 (2) Åθ = 3.1–27.5°
b = 22.1762 (6) ŵ = 0.14 mm1
c = 8.1006 (2) ÅT = 120 K
β = 96.4890 (16)°Block, yellow
V = 1330.35 (6) Å30.28 × 0.16 × 0.16 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
3028 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode2754 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 98
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2826
Tmin = 0.932, Tmax = 0.979l = 1010
16762 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0419P)2 + 0.7643P]
where P = (Fo2 + 2Fc2)/3
3028 reflections(Δ/σ)max = 0.001
217 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C13H9N5O6V = 1330.35 (6) Å3
Mr = 331.25Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.4534 (2) ŵ = 0.14 mm1
b = 22.1762 (6) ÅT = 120 K
c = 8.1006 (2) Å0.28 × 0.16 × 0.16 mm
β = 96.4890 (16)°
Data collection top
Nonius KappaCCD
diffractometer
3028 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2754 reflections with I > 2σ(I)
Tmin = 0.932, Tmax = 0.979Rint = 0.035
16762 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.06Δρmax = 0.30 e Å3
3028 reflectionsΔρmin = 0.22 e Å3
217 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.29107 (15)0.77611 (5)0.18882 (14)0.0198 (2)
C120.29407 (18)0.76568 (6)0.35161 (16)0.0194 (3)
C130.37705 (18)0.71574 (6)0.43050 (16)0.0185 (3)
C140.45741 (17)0.67366 (5)0.33512 (16)0.0167 (3)
C150.45568 (17)0.68411 (6)0.16552 (16)0.0197 (3)
C160.37324 (19)0.73597 (6)0.09849 (16)0.0217 (3)
C170.53402 (17)0.61583 (6)0.40841 (16)0.0180 (3)
O10.52800 (14)0.56838 (4)0.32958 (13)0.0262 (2)
N170.60258 (15)0.61959 (5)0.56963 (13)0.0176 (2)
N270.68100 (15)0.56676 (5)0.63692 (14)0.0190 (2)
C270.69292 (17)0.55863 (6)0.80285 (16)0.0174 (3)
O20.64901 (14)0.59731 (4)0.89848 (12)0.0246 (2)
C210.77229 (16)0.49956 (5)0.86527 (16)0.0164 (3)
C220.86809 (17)0.46194 (6)0.76805 (16)0.0177 (3)
C230.93238 (16)0.40760 (6)0.83413 (16)0.0177 (3)
N31.03185 (15)0.36794 (5)0.73068 (14)0.0211 (2)
O311.06419 (15)0.38698 (5)0.59570 (14)0.0331 (3)
O321.07576 (15)0.31778 (5)0.78513 (13)0.0310 (3)
C240.90610 (17)0.38855 (6)0.99209 (17)0.0192 (3)
C250.81494 (17)0.42775 (6)1.08553 (16)0.0180 (3)
N50.78968 (16)0.40949 (5)1.25585 (15)0.0234 (3)
O510.80620 (16)0.35600 (5)1.29025 (14)0.0347 (3)
O520.75444 (15)0.44909 (5)1.35295 (13)0.0307 (3)
C260.74794 (16)0.48310 (6)1.02698 (16)0.0173 (3)
H120.23650.79390.41660.023*
H130.37880.71050.54710.022*
H150.50990.65630.09710.024*
H160.37490.74350.01680.026*
H170.65470.65340.60640.021*
H270.68330.53710.56500.023*
H220.88860.47350.65880.021*
H240.94850.35051.03410.023*
H260.68710.50911.09550.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0221 (6)0.0157 (5)0.0209 (5)0.0002 (4)0.0002 (4)0.0024 (4)
C120.0221 (6)0.0149 (6)0.0213 (6)0.0000 (5)0.0034 (5)0.0003 (5)
C130.0218 (6)0.0169 (6)0.0168 (6)0.0004 (5)0.0020 (5)0.0011 (5)
C140.0167 (6)0.0131 (6)0.0197 (6)0.0022 (4)0.0005 (5)0.0004 (5)
C150.0207 (6)0.0192 (6)0.0190 (6)0.0006 (5)0.0017 (5)0.0030 (5)
C160.0265 (7)0.0211 (6)0.0173 (6)0.0009 (5)0.0011 (5)0.0013 (5)
C170.0179 (6)0.0151 (6)0.0202 (6)0.0002 (5)0.0006 (5)0.0015 (5)
O10.0325 (6)0.0161 (5)0.0274 (5)0.0037 (4)0.0075 (4)0.0062 (4)
N170.0217 (5)0.0105 (5)0.0196 (5)0.0013 (4)0.0015 (4)0.0006 (4)
N270.0249 (6)0.0120 (5)0.0195 (5)0.0033 (4)0.0003 (4)0.0001 (4)
C270.0163 (6)0.0149 (6)0.0210 (6)0.0009 (4)0.0027 (5)0.0014 (5)
O20.0351 (6)0.0174 (5)0.0224 (5)0.0060 (4)0.0084 (4)0.0015 (4)
C210.0153 (6)0.0137 (6)0.0195 (6)0.0021 (4)0.0009 (5)0.0003 (5)
C220.0168 (6)0.0170 (6)0.0189 (6)0.0013 (5)0.0003 (5)0.0006 (5)
C230.0150 (6)0.0158 (6)0.0223 (6)0.0004 (5)0.0014 (5)0.0024 (5)
N30.0194 (5)0.0193 (5)0.0243 (6)0.0020 (4)0.0009 (4)0.0024 (4)
O310.0380 (6)0.0337 (6)0.0304 (6)0.0099 (5)0.0163 (5)0.0044 (5)
O320.0424 (6)0.0201 (5)0.0302 (6)0.0114 (4)0.0025 (5)0.0013 (4)
C240.0173 (6)0.0149 (6)0.0246 (7)0.0009 (5)0.0003 (5)0.0018 (5)
C250.0182 (6)0.0171 (6)0.0187 (6)0.0025 (5)0.0015 (5)0.0024 (5)
N50.0242 (6)0.0233 (6)0.0232 (6)0.0026 (5)0.0053 (5)0.0061 (5)
O510.0456 (7)0.0243 (5)0.0364 (6)0.0059 (5)0.0148 (5)0.0144 (5)
O520.0395 (6)0.0319 (6)0.0217 (5)0.0083 (5)0.0073 (4)0.0017 (4)
C260.0160 (6)0.0160 (6)0.0198 (6)0.0016 (5)0.0010 (5)0.0007 (5)
Geometric parameters (Å, º) top
N11—C121.3366 (17)C27—O21.2249 (16)
N11—C161.3432 (17)C27—C211.5012 (17)
C12—C131.3885 (18)C21—C261.3914 (18)
C12—H120.95C21—C221.3976 (18)
C13—C141.3897 (18)C22—C231.3822 (18)
C13—H130.95C22—H220.95
C14—C151.3919 (18)C23—C241.3823 (18)
C14—C171.4988 (17)C23—N31.4718 (16)
C15—C161.3856 (19)N3—O311.2213 (16)
C15—H150.95N3—O321.2272 (15)
C16—H160.95C24—C251.3808 (18)
C17—O11.2292 (16)C24—H240.95
C17—N171.3501 (17)C25—C261.3883 (18)
N17—N271.3926 (14)C25—N51.4702 (17)
N17—H170.8801N5—O511.2216 (15)
N27—C271.3491 (17)N5—O521.2270 (16)
N27—H270.8796C26—H260.95
C12—N11—C16117.71 (11)O2—C27—C21121.42 (12)
N11—C12—C13123.30 (12)N27—C27—C21115.55 (11)
N11—C12—H12118.4C26—C21—C22120.21 (12)
C13—C12—H12118.4C26—C21—C27117.23 (11)
C12—C13—C14118.51 (12)C22—C21—C27122.55 (11)
C12—C13—H13120.7C23—C22—C21118.63 (12)
C14—C13—H13120.7C23—C22—H22120.7
C13—C14—C15118.71 (12)C21—C22—H22120.7
C13—C14—C17121.55 (11)C22—C23—C24123.07 (12)
C15—C14—C17119.61 (11)C22—C23—N3118.39 (12)
C16—C15—C14118.64 (12)C24—C23—N3118.54 (11)
C16—C15—H15120.7O31—N3—O32124.31 (12)
C14—C15—H15120.7O31—N3—C23117.79 (11)
N11—C16—C15123.09 (12)O32—N3—C23117.90 (11)
N11—C16—H16118.5C25—C24—C23116.43 (12)
C15—C16—H16118.5C25—C24—H24121.8
O1—C17—N17122.89 (12)C23—C24—H24121.8
O1—C17—C14122.47 (12)C24—C25—C26123.34 (12)
N17—C17—C14114.58 (11)C24—C25—N5117.65 (11)
C17—N17—N27115.02 (10)C26—C25—N5119.00 (11)
C17—N17—H17119.0O51—N5—O52124.90 (12)
N27—N17—H17115.7O51—N5—C25117.47 (11)
C27—N27—N17118.68 (10)O52—N5—C25117.63 (11)
C27—N27—H27123.8C25—C26—C21118.26 (12)
N17—N27—H27114.1C25—C26—H26120.9
O2—C27—N27122.97 (12)C21—C26—H26120.9
C16—N11—C12—C130.13 (19)C26—C21—C22—C232.04 (18)
N11—C12—C13—C141.6 (2)C27—C21—C22—C23178.31 (11)
C12—C13—C14—C151.72 (19)C21—C22—C23—C240.13 (19)
C12—C13—C14—C17174.12 (12)C21—C22—C23—N3179.50 (11)
C13—C14—C15—C160.25 (19)C22—C23—N3—O315.25 (18)
C17—C14—C15—C16175.67 (12)C24—C23—N3—O31175.36 (12)
C12—N11—C16—C151.7 (2)C22—C23—N3—O32174.27 (12)
C14—C15—C16—N111.6 (2)C24—C23—N3—O325.13 (18)
C13—C14—C17—O1145.18 (14)C22—C23—C24—C251.78 (19)
C15—C14—C17—O130.62 (19)N3—C23—C24—C25178.86 (11)
C13—C14—C17—N1732.02 (17)C23—C24—C25—C261.34 (19)
C15—C14—C17—N17152.18 (12)C23—C24—C25—N5178.23 (11)
O1—C17—N17—N275.43 (19)C24—C25—N5—O5118.90 (18)
C14—C17—N17—N27177.39 (10)C26—C25—N5—O51161.51 (12)
C17—N17—N27—C27156.24 (12)C24—C25—N5—O52160.78 (12)
N17—N27—C27—O25.06 (19)C26—C25—N5—O5218.81 (18)
N17—N27—C27—C21177.66 (10)C24—C25—C26—C210.72 (19)
O2—C27—C21—C2617.69 (18)N5—C25—C26—C21179.71 (11)
N27—C27—C21—C26164.99 (11)C22—C21—C26—C252.44 (18)
O2—C27—C21—C22161.97 (12)C27—C21—C26—C25177.90 (11)
N27—C27—C21—C2215.36 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N17—H17···N11i0.881.942.8194 (16)175
C12—H12···O2ii0.952.503.2615 (16)137
C13—H13···O51iii0.952.493.1956 (17)131
C15—H15···O2iv0.952.403.3415 (16)172
Symmetry codes: (i) x+1/2, y+3/2, z+1/2; (ii) x1/2, y+3/2, z1/2; (iii) x+1, y+1, z+2; (iv) x, y, z1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H10ClN4O4+·ClC13H9N5O6
Mr357.15331.25
Crystal system, space groupOrthorhombic, Aba2Monoclinic, P21/n
Temperature (K)120120
a, b, c (Å)15.2414 (2), 22.6430 (9), 8.3783 (5)7.4534 (2), 22.1762 (6), 8.1006 (2)
α, β, γ (°)90, 90, 9090, 96.4890 (16), 90
V3)2891.4 (2)1330.35 (6)
Z84
Radiation typeMo KαMo Kα
µ (mm1)0.480.14
Crystal size (mm)0.30 × 0.10 × 0.100.28 × 0.16 × 0.16
Data collection
DiffractometerNonius KappaCCD
diffractometer
Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.870, 0.9540.932, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
14651, 3204, 3013 16762, 3028, 2754
Rint0.0440.035
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.074, 1.05 0.037, 0.099, 1.06
No. of reflections32043028
No. of parameters208217
No. of restraints10
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.360.30, 0.22
Absolute structureFlack (1983), 1424 Friedel pairs?
Absolute structure parameter0.01 (5)?

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N11—H11···Cl10.882.263.078 (2)153
N17—H17···Cl1i0.882.313.161 (2)163
N27—H27···Cl1ii0.882.333.176 (2)162
C12—H12···O31iii0.952.393.127 (3)134
C16—H16···O2ii0.952.272.988 (3)132
C16—H16···O32iv0.952.423.018 (2)121
C25—H25···O1v0.952.503.439 (3)168
C26—H26···O2vi0.952.333.204 (2)152
C13—H13···Cl1i0.952.673.607 (2)170
C22—H22···Cl1ii0.952.673.589 (2)162
Symmetry codes: (i) x+1/2, y+3/2, z; (ii) x+1/2, y, z+1/2; (iii) x+1, y+3/2, z1/2; (iv) x1, y, z; (v) x+1/2, y+1, z1/2; (vi) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N17—H17···N11i0.881.942.8194 (16)175
C12—H12···O2ii0.952.503.2615 (16)137
C13—H13···O51iii0.952.493.1956 (17)131
C15—H15···O2iv0.952.403.3415 (16)172
Symmetry codes: (i) x+1/2, y+3/2, z+1/2; (ii) x1/2, y+3/2, z1/2; (iii) x+1, y+1, z+2; (iv) x, y, z1.
Selected torsion angles (°) for compounds (I) and (II) top
Parameter(I)(II)
C13-C14-C17-N171.8 (3)-32.02 (17)
C14-C17-N17-N27-172.91 (17)-177.39 (10)
C17-N17-N27-C2777.4 (3)-156.24 (12)
N17-N27-C27-C21170.59 (16)177.66 (10)
N27-C27-C21-C22-14.3 (3)15.36 (17)
C22-C23-N3-O31-15.8 (3)5.25 (18)
C24-C25-N5-O51-18.90 (18)
 

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
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First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
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First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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